Beta-diketiminate precursors for metal containing film deposition

Abstract

Methods and compositions for depositing a metal containing film on a substrate are disclosed. A reactor, and at least one substrate disposed in the reactor, are provided. A metal containing precursor with at least one β-diketiminate ligand is provided and introduced into the reactor, which is maintained at a temperature of at least 100° C. Metal is deposited onto the substrate through a deposition process to form a thin film on the substrate.

1 . A method of forming a metal containing film on a substrate, comprising:
 a) providing a reactor and at least one substrate disposed therein;   b) introducing a first metal containing precursor into the reactor, wherein the first metal containing precursor has the general formula (I):   
     
       
         
         
             
             
         
       
       
         wherein:
 M is a metal selected from the group consisting of: alkaline earth metals; scandium; yttrium; a lanthanide; titanium; zirconium; hafnium; and combinations thereof: 
 each L is independently an anionic ligand; 
 each Y is independently a neutral ligand; 
 R2, R3, and R4 are independently selected from hydrogen and methyl; 
 R1 and R5 are independently selected from methyl, ethyl, isopropyl, tert-butyl and combinations thereof 
 n is the valance state of M; 
 0≦z≦5; and 
 1≦x≦n; 
 
       
       C) maintaining the reactor at a temperature of at least about 100° C.; and 
       d) contacting the first metal containing precursor with the substrate to form a metal containing film. 
     
   
   
       2 . The method of  claim 1 , wherein L is at least one member selected from the group consisting of: a halide; an alkoxide group; an amide group; a mercaptide group; cyanide; an alkyl group; an amidinate group; a cylcopentadienyl; a guanidinate group; an isoureate group; a β-diketiminate group; a β-diketoiminate group; and combinations thereof. 
   
   
       3 . The method of  claim 1 , wherein at least one L is a β-diketiminate group with a structure that is the same as the β-diketiminate ligand in formula (I). 
   
   
       4 . The method of  claim 1 , wherein at least one L is a β-diketiminate group with a structure that is different than the β-diketiminate ligand in formula (I). 
   
   
       5 . The method of  claim 1 , wherein M is calcium, strontium or barium. 
   
   
       6 . The method of  claim 1 , wherein Y is at least one member selected from the group consisting of: a carbonyl; a nitrosyl; ammonia; an amine; nitrogen; a phosphine; an alcohol; water; tetrahydrofuran (THF); and combinations thereof. 
   
   
       7 . The method of  claim 1 , further comprising:
 a) introducing a second metal containing precursor into the reactor, wherein the second metal containing precursor is different from the first precursor; and   b) contacting the second metal containing precursor with the substrate to form a metal containing film.   
   
   
       8 . The method of  claim 7 , wherein the metal in the second metal containing precursor is at least one member selected from the group consisting of: titanium; tantalum; bismuth; hafnium; zirconium; lead; niobium; magnesium; aluminum; and combinations thereof. 
   
   
       9 . The method of  claim 1 , further comprising maintaining the reactor at a temperature between about 100° C. to about 500° C. 
   
   
       10 . The method of  claim 9 , further comprising maintaining the reactor at a temperature between about 150° C. and about 350° C. 
   
   
       11 . The method of  claim 1 , further comprising maintaining the reactor at a pressure between about 1 Pa and about 10 5  Pa. 
   
   
       12 . The method of  claim 11 , further comprising maintaining the reactor at a pressure between about 25 Pa and about 10 3  Pa. 
   
   
       13 . The method of  claim 1 , further comprising introducing at least one reducing gas into the reactor, wherein the reducing gas comprises at least one member selected from the group consisting of H 2 ; NH 3 ; SiH 4 ; Si 2 H 6 ; Si 3 H 8 ; SiH 2 Me 2 , SiH 2 Et 2 , N(SiH 3 ) 3 , hydrogen radicals; and mixtures thereof. 
   
   
       14 . The method of  claim 13 , wherein the first metal containing precursor and the reducing gas are introduced into the chamber either substantially simultaneously, or sequentially. 
   
   
       15 . The method of  claim 13 , wherein the first metal containing precursor and the reducing gas are introduced into the chamber substantially simultaneously, and the chamber is configured for chemical vapor deposition. 
   
   
       16 . The method of  claim 13 , wherein the first metal containing precursor and the reducing gas are introduced into the chamber sequentially, and the chamber is configured for atomic layer deposition. 
   
   
       17 . The method of  claim 1 , further comprising introducing at least one oxidizing gas into the reactor, wherein the oxidizing gas comprises at least one member selected from the group consisting of: O 2 ; O 3 ; H 2 O; NO; oxygen radicals; and mixtures thereof. 
   
   
       18 . The method of  claim 17 , wherein the first metal containing precursor and the oxidizing gas are introduced into the chamber either substantially simultaneously, or sequentially. 
   
   
       19 . The method of  claim 17 , wherein the first metal containing precursor and the oxidizing gas are introduced into the chamber substantially simultaneously, and the chamber is configured for chemical vapor deposition. 
   
   
       20 . The method of  claim 17 , wherein the first metal containing precursor and the oxidizing gas are introduced into the chamber sequentially, and the chamber is configured for atomic layer deposition. 
   
   
       21 . The method of  claim 1 , wherein the first metal containing precursor comprises at least one member selected from the group consisting of: tri-(4-N-ethylamino-3-penten-2-N-ethyliminato)titanium; (4-di-(4-N-tertbutylamino-3-penten-2-N-tertbutyliminato)strontium; di-(4-N-tertbutylamino-3-penten-2-N-tertbutyliminato)calcium; di-(4-N-tertbutylamino-3-penten-2-N-tertbutyliminato)barium; di-(4-N-isopropylamino-3-penten-2-N-isopropyliminato)strontium; and di-(4-N-isopropylamino-3-penten-2-N-isopropyliminato)calcium. 
   
   
       22 . A metal containing thin film coated substrate comprising the product of the method of  claim 1 . 
   
   
       23 . A composition comprising a metal containing precursor of the general formula: 
     
       
         
         
             
             
         
       
     
     wherein:
 M is a metal selected from the group consisting of: alkaline earth metals; scandium; yttrium; a lanthanide; titanium; zirconium; 
 hafnium; and combinations thereof: 
 each L is independently an anionic ligand; 
 each Y is independently a neutral ligand; 
 R2, R3, and R4 are independently selected from hydrogen and methyl; 
 R1, R1 and R5 are independently selected from methyl, ethyl, isopropyl, tert-butyl and combinations thereof 
 n is the valance state of M; 
 0≦z≦5; and 
 1≦x≦n. 
 
   
   
       24 . The composition of  claim 23 , comprising at least one member selected from the group consisting of: tri-(4-N-ethylamino-3-penten-2-N-ethyliminato)titanium; and (4-N-ethylamino-3-penten-2-N-ethyliminato)-tri(dimethylamino)zirconium.